This invention is generally directed to developer compositions, and more specifically, the present invention relates to developer compositions with coated carrier particles prepared by dry powder processes. In embodiments of the present invention, the carrier particles are comprised of a core with coating thereover generated from certain polyester resins, especially crosslinked polyesters as illustrated in U.S. Pat. Nos. 5,376,494 and 5,227,560, the disclosures of which are totally incorporated herein by reference. Moreover, in another embodiment of the present invention the carrier particles are prepared by a dry coating process wherein the crosslinked polymer is applied to the carrier enabling insulating particles with relatively constant conductivity parameters; and also wherein the triboelectric charge on the carrier can vary significantly depending on the coatings selected. Developer compositions comprised of the carrier particles prepared by the dry coating process of the present invention are useful in electrostatographic or electrophotographic imaging systems, especially xerographic imaging and printing processes. Additionally, developer compositions comprised of substantially insulating carrier particles prepared in accordance with the process of the present invention are useful in imaging methods wherein relatively constant conductivity parameters are desired. Furthermore, in the aforementioned imaging processes the triboelectric charge on the carrier particles can be preselected depending on the polymer composition applied to the carrier core. The reactive extruded polyesters selected as a carrier coating in embodiments of the present invention are jettable binder polymers; and moreover, the aforementioned coatings, which can be selected with gel contents of up to about 45 percent, and preferably from about 20 to about 40 percent, have no, or minimal emission on melting, and these coatings possess excellent mechanical toughness. Further, in embodiments the reactive extruded polyester coatings of the present invention can be utilized as a contrast carrier coating, can be selected as one component of a coating carrier mixture, and can contain dispersed therein conductive components, such as conductive carbon blacks or metal oxides in amounts, for example, of from about 1 to about 70, and preferably from about 20 to about 60 weight percent. Moreover, the triboelectric characteristics of the coated carrier can be altered and the conductivity increased by the addition to the carrier coating, or coatings of conductive components, such as carbon black, metal oxides like tin oxide, charge additives, such as distearyl dimethyl ammonium methyl sulfate (DDAMS), azo complexes, such as bis[1-[(3,5-disubstituted-2-hydroxyphenyl)azo]-3-(mono-substituted)-2-naph thalenolato(2-)] chromate(1-), ammonium sodium and hydrogen (TRH), and other known toner charge additives, and the like. Also, in embodiments of the present invention the carrier coating characteristics can be modified by adding during the preparation thereof an initiator, such as benzoyl peroxide, to, for example, promote further crosslinking of the reactive extruded polyester.
The electrostatographic process, and particularly the xerographic process, is well known. This process involves the formation of an electrostatic latent image on a photoreceptor, followed by development, and subsequent transfer of the image to a suitable substrate. Numerous different types of xerographic imaging processes are known wherein, for example, insulative developer particles or conductive toner compositions are selected depending on the development systems used. Moreover, of importance with respect to the aforementioned developer compositions is the appropriate triboelectric charging values associated therewith as it is these values that enable continued constant developed images of high quality and excellent resolution.
Additionally, carrier particles for use in the development of electrostatic latent images are described in many patents including, for example, U.S. Pat. No. 3,590,000. These carrier particles may consist of various cores, including steel, with a coating thereover of fluoropolymers, and terpolymers of styrene, methacrylate, and silane compounds. Past efforts have focused on the attainment of coatings for carrier particles for the purpose of improving development quality, and also to permit particles that can be recycled, and that do not adversely effect the imaging member in any substantial manner. Many of the present commercial coatings can deteriorate rapidly, especially when selected for a continuous xerographic process where the entire coating may separate from the carrier core in the form of chips or flakes; and fail upon impact, or abrasive contact with machine parts and other carrier particles. These flakes or chips, which cannot generally be reclaimed from the developer mixture, have an adverse effect on the triboelectric charging characteristics of the carrier particles thereby providing images with lower resolution in comparison to those compositions wherein the carrier coatings are retained on the surface of the core substrate. Further, another problem encountered with some prior art carrier coatings resides in fluctuating triboelectric charging characteristics, particularly with changes in relative humidity. The aforementioned modification in triboelectric charging characteristics provides developed images of lower quality, and with background deposits.
There are also illustrated in U.S. Pat. No. 4,233,387, the disclosure of which is totally incorporated herein by reference, coated carrier components for electrostatographic developer mixtures comprised of finely divided toner particles clinging to the surface of the carrier particles. Specifically, there is disclosed in this patent coated carrier particles obtained by mixing carrier core particles of an average diameter of from between about 30 microns to about 1,000 microns with from about 0.05 percent to about 3.0 percent by weight, based on the weight of the coated carrier particles, of thermoplastic resin particles. The resulting mixture is then dry blended until the thermoplastic resin particles adhere to the carrier core by mechanical impaction, and/or electrostatic attraction. Thereafter, the mixture is heated to a temperature of from about 320.degree. F. to about 650.degree. F. for a period of 20 minutes to about 120 minutes, enabling the thermoplastic resin particles to melt and fuse on the carrier core. While the developer and carrier particles prepared in accordance with the process of this patent, the disclosure of which has been totally incorporated herein by reference, are suitable for their intended purposes, the conductivity values of the resulting particles are not constant in all instances, for example, when a change in carrier coating weight is accomplished to achieve a modification of the triboelectric charging characteristics; and further with regard to the '387 patent, in many situations carrier and developer mixtures with only specific triboelectric charging values can be generated when certain conductivity values or characteristics are contemplated. With the invention of the present application, the conductivity of the resulting carrier particles are substantially constant, and moreover, the triboelectric values can be selected to vary significantly, for example, from less than -10 microcoulombs per gram of charge imparted to the toner to greater than -70 microcoulombs per gram, depending on the polymer mixture selected for affecting the coating processes.
There is illustrated in U.S. Pat. Nos. 4,937,166 and 4,935,326, the disclosures of which are totally incorporated herein by reference, carrier containing a mixture of polymers, such as two polymers, not in close proximity in the triboelectric series.
The present invention in embodiments provides numerous advantages and efficiencies over the prior art. Among those advantages are the following:
1) Additives or combination of additives, such as conductive carbon blacks, conductive metal oxides including tin oxide, charge control agents including distearyl dimethyl ammonium methyl sulfate (DDAMS), bis[1-[(3,5-disubstituted-2-hydroxyphenyl)azo]-3-(mono-substituted)-2-naph thalenolato(2-)] chromate(1-), ammonium sodium and hydrogen (TRH), cetyl pyridinium chloride (CPC), and benzoic acid, 2-[6-(ethylamino)-3-(ethylamino)-2,7-dimethyl-3H-xanthen-9-yl]-ethyl ester, compound with molybedenum tungsten hydroxide oxide phosphate or FANAL PINK.RTM. D4830 can be incorporated into the polymer in effective amounts, such as about 1 weight percent, by known melt mix and particle size attrition techniques to modify the carrier triboelectric and conductivity properties of the polymer. This eliminates the need to redesign the chemical process by which the polymer is generated for incorporation of additional or different components therein or thereon.
2) The rheological properties of the polymer, which control both the ability of the polymer to coat the carrier surface and the mechanical toughness of the carrier coating, are controlled by altering the polymer gel content by known melt mix techniques and are tunable over the range indicated above. This eliminates the need to redesign the chemical process by which the polymer is prepared to alter the rheological properties of the polymer.
3) The use of a single crosslinked polyester host polymer to generate all of the polymer composites by incorporation of additives, such as conductive carbon blacks, conductive metal oxides including tin oxide, charge control agents including distearyl dimethyl ammonium methyl sulfate (DDAMS), bis[1-[(3,5-disubstituted-2-hydroxyphenyl)azo]-3-(monosubstituted)-2-napht halenolato(2-)] chromate(1-), ammonium sodium and hydrogen (TRH), cetyl pyridinium chloride (CPC), and benzoic acid, 2-[6-(ethylamino)-3-(ethylamino)-2,7-dimethyl-3H-xanthen-9-yl]-ethyl ester, compound with molybedenum tungsten hydroxide oxide phosphate (FANAL PINK.RTM. D4830) to control the carrier triboelectric charge over the range of from about -7 to about -70 microcoulombs per gram, and the carrier conductivity over the range of from about 10.sup.-15 mho/cm to about 10.sup.-6 mho/cm which ensures the miscibility of two (or more) polymers at a given carrier processing temperature, such as from about 320.degree. F. to about 650.degree. F., which are two polymers ratioed at from about 10 percent to about 90 percent of the first polymer coating and from about 90 to about 10 percent of the second polymer coating, to control either the carrier triboelectric or carrier conductivity properties.
4) No solvents are needed in either the manufacture of the crosslinked resin, the polymer composite or the coated carrier, reducing emission of volatile organic compounds (VOCs) to a minimum.
With further reference to the prior art, carriers obtained by applying insulating resinous coatings to porous metallic carrier cores using solution coating techniques are undesirable from many viewpoints. For example, the coating material will usually reside in the pores of the carrier cores, rather than at the surfaces thereof; and, therefore, is not available for triboelectric charging when the coated carrier particles are mixed with finely divided toner particles. Attempts to resolve this problem by increasing the carrier coating weights, for example, to as much as 3 percent or greater to provide an effective triboelectric coating to the carrier particles necessarily involves handling excessive quantities of solvents, and further, usually these processes result in low product yields. Also, solution coated carrier particles, when combined and mixed with finely divided toner particles, provide in some instances triboelectric charging values which are too low for many uses. The powder coating processes of the present invention overcome these disadvantages, and further enable developers that are capable of generating high and useful triboelectric charging values with finely divided toner particles; and also wherein the carrier particles are of substantially constant conductivity. Further, when resin coated carrier particles are prepared by the powder coating process of the present invention, the majority of the coating materials are fused to the carrier surface thereby reducing the number of toner impaction sites on the carrier material. Additionally, there can be achieved with the process of the present invention, and the carriers thereof, independent of one another, desirable triboelectric charging characteristics and conductivity values; that is, for example the triboelectric charging parameter is not dependent on the carrier coating weight as is believed to be the situation with the process of U.S. Pat. No. 4,233,387 wherein an increase in coating weight on the carrier particles may function to also permit an increase in the triboelectric charging characteristics. Specifically, therefore, with the carrier compositions and process of the present invention there can be formulated developers with selected triboelectric charging characteristics and/or conductivity values in a number of different combinations.
Thus, for example, there can be formulated in accordance with the invention of the present application developers with conductivities of from about 10.sup.-6 mho (cm).sup.-1 to 10.sup.-17 mho (cm).sup.-1 as determined in a magnetic brush conducting cell, and triboelectric charging values of from about a -7 to a -70, and in embodiments from about -10 to about -30 microcoulombs per gram on the carrier particles as determined by the known Faraday Cage technique. Thus, the developers of the present invention can be formulated with constant conductivity values with different triboelectric charging characteristics by, for example, maintaining the same total coating weight on the carrier particles and changing the ratio of two (or more) polymers which comprise the coating. Similarly, there can be formulated developer compositions wherein constant triboelectric charging values are achieved and the conductivities are altered by retaining the same total coating weight on the carrier particles and changing the ratio of two (or more) polymers which comprise the coating.
Other patents of interest include U.S. Pat. No. 3,939,086, which teaches steel carrier beads with polyethylene coatings, see column 6; U.S. Pat. No. 4,264,697, which discloses dry coating and fusing processes; U.S. Pat. Nos. 3,533,835; 3,658,500; 3,798,167; 3,918,968; 3,922,382; 4,238,558; 4,310,611; 4,397,935; and 4,434,220, the disclosures of each of these patents being totally incorporated herein by reference.